Printing and pad-dyeing of polyacrylonitrile articles



U ed S es Pa e AND PAD-DYEINd oFroLYAcRYLo- PRINTING g NrrRI nAnrrcLnsWalter Fluegel and Arnold Dii rsh' Basel, Switzerland,

'assignors'to Sandoz Ltd. Basel, Switzerland No Drawing. FiledNomi-5,1958, Ser. No. 776,211

Claims priority, application Germany lune 11, 1954 11 Claims. (Cl. 8-62) The present invention is a continuation-in-part application to theco-pending application Ser. No. 496,949, filed on March 25, 1955, nowabandoned, and relates to a process'for the printing or pad-dyeing ofsubstrates consisting essentially of polyacrylonitril e.

It has been found thatparticularly good results in 2,955,010 PatentedOct. 4, 1960 A fabric of polyacrylonitrile staple fiber (Orlon 42) isprinted with a paste of the following composition:

' Parts Xylene Light Yellow R 160% (Schultz Farbstofftabellen N0. 736)15 Thiodiethylene glycol 50 Water 325 Crystal gum 1: 500

Tartaric acid 1:1 60

Cuprous oxide 1:1 50

printing or pad-dyeing of polyacrylonitrile substrates are obtained byimpregnating the said substrates with aqueous pastes or liquorscontaining a water-soluble organic dyestuff, e.g. a direct dyestuff, anacid dyestuli, a metallizable dyestuff or a metallized dyestuif, awater-soluble organic solvent, a thickener, cuprous oxide, preferablypresent in finely dispersed form and a non-volatile acid i or theammonium salt thereof, and subsequently drying and steaming theresulting prints and pad-dyeings.

The polyacrylonitrile substrates can be printed in fabric or in slubbingform and pad-dyed in' fabric form. The acid dyestuffs are preferablychosen from the group of the acid anthraquinone and acid azo dyestuffs.The metallizable dyestuffs possess met'allizable groupings of theformula wherein x represents a hydroxy, carboxylic acid or an aminogroup which latter may be substituted, and/or lake-formingortho-hydroxy-carboxylic acid groupings, or lake-forming ortho-dihydroxygroupings. Drying of the printings or pad-dyeings is carried outpreferably at 140-160 F., steaming at 220265 F. The steaming temperatureis determined by the physical properties of .the printed or pad-dyedmaterial; under no circumstances should it reach or exceed the meltingtemperature of the substrate.

The present invention also relates to the aqueous comthereof, f.i.ammonium sulfate or phosphate, tartaric.

or slubbing good printed or pad dyed with a weakly acid 81) yarn isprinted with a paste containing:

The print is dried and steamed for 30 minutes at 225- 230, then rinsedcold and soaped at -140 with a sulphonated fatty alcohol. Given verygood penetration of the fabric, a deep yellow print is obtained which istrueto shade and has very good wet fastness properties.

A full violet print is obtained when using, instead of ,15 parts ofXylene Light Yellow R 15 parts of Omega Chrome Violet B (SchultzFarbstofitabellen, 7th impression, volume II, p. 161).

By replacing the 15 parts of Xylene Light Yellow R 160% by 20 parts ofthe copper complex compound of the monoazo dyestuff obtained by couplingdiazotized Z-amino-l-hydroxy-S,4,6-trichlorobenzene with l-amino- '8hydroxynaphthalene-2,4-disulfonic acid, a brilliant blue print results.

Example 2 A fabric of polyacrylonitrile endless filament (Orlon PartsOmega Chrome Yellow ME (Schultz Farbstoiftabellen, 7th impression,additional volume H,

After drying the print is steamed for 20 minutes at 260, rinsed in coldwater, soaped and again rinsed cold. Upon drying, an attractive yellowprint'is obtained; the penetration of the fabric is very good.

By replacing the 15 parts of Omega Chrome Yellow ME by 20 parts of OmegaChrome Red B (Schultz Farbstotftabellen, No. 742), a full fast red printis obtained.

A brown print results when 20 parts of coppered 2,4 diamino 2 hydroxy 5'nitro 1,1 azobenzene 5 sulfonic acid is used instead of 15 parts ofOmega Chrome Yellow ME.

yieldsha violet print. Omega Chrome Red G (Schultz Farbstofitabellen,7th

. 3 p impression, volume II, p. 161) and Omega Chrome Orange ML (SchultzFarbstoiftabellen, 7th impression, volume 11, p. 222) are similarlyprinted.

Example 3 Slubbing of polyacrylonitrile staple fiber is printed with apaste of the following composition:

Parts Alizarine Red SZ (Schultz- Farbstofitabellen" No, Q' 1: Butyl(Earbitol 50 Water 500 Industrialgum 1:2 300 Lactic acid 121 Q p 60Guprous oxide 1 :1 60

The print is steamed; for 3Q-minutes at 220, rinsed cold; soaped at- 120with a sulphonated' fatty alcohol, rinsed again cold and dried. A fullyellow print having y ood fa n ss prop rties is btained y replac ng hev.0 parts of. Ali arine Red Z by 8 ing. the.v ob ained. print. for 210tea at. 26.0" rins n cold andsoauin i a fast attractive rey.militia-obtained- Yellow and scarle prints. are bta ned when incomrating into the printing paste, instead of 30 parts of Aliz arine RedSZ, 30 parts of the sodium salt of 5-propionylamino-l'.9-isothiazolanthrone 1 sulfonic acid and 30 parts ofthe lithium salt of 3"-benzoyl-.4-aminol--.9-anthrapyridone-Zsulfonicacid respectively.

Example 4 r Par Potassium salt of 1.4-diaminoanthraquinoneaz-sul tonicacid t, t i V 15 Pyridine 100 Hotwat .7 565 CrystaIg m, 2 2.00Citrioacid 1:1 r r t Cuprous oxid 111. -.,-"fin-ufiu-samfi-a 60 Apadding liquor prepared with these ingredients is appl e n afabria ofpolya ryloni le sta lefiben Th padded fabric is drie and steam d for.2.0 minutes at about 230 and 0.5 superatmospheric pressure. After anintermediate rinse with old, water, it issoaped at 140? with a, fattyacid condensate, rinsed again and dried.

The full violet pad-dyeing thus produced is fastto light,

washing and rubbing.

If, instead of 15 parts of the potassium salt of 1,4-diaminoanthraquinone-Zsulfonic acid, 15 parts. of the sodium salt of1-amino-4-(4'-acetylamino) phenylaminoanthraquinone-2.7-disulfonic acidare used, a pad-dyeing in a full blue shade of excellent fastnessproperties yields.

A green pad-dyeing is obtained byv incorporating into thepadding liquor30 partsof thepotassium salt of 1.4-

di-(fii-rnethyl)-phenylaminoanthraquinonee disulfonic acid.

Example A fabric of po y srylon trle staple fiber s p nted with a. pasteof the following composition:

' Parts Sodium salt of S-sulfoacetylamino-l.9-isothiazob The print isdried, steamed for 10 minutes at 220 without pressure and for 20 minutesat about- 230"- and at 0.5 superatmospheric pressure, then rinsed wellwith cold water, soaped at 140 with a fatty acid condensate and rinsedagain. A full yellow print of very good fastness to light, washing andrubbing is obtained.

Also yellow print results, when the 30 parts of the sodium salt of5-sulfoacetyla-mino-1.9-isothiazolanthrone are replaced by 30 parts of4.4'-dihydroxy-5-sulfo-l.1- azobenezne-3.3'-dicarboxylic acid, or themonoazo dyestuff obtained by coupling diazotized 2-amino-1-carboxy-2.4.2' trihydroxy 3" sulfo 5' -chloro-1a1' azoenzanesi-carbosrliaadd; yilds; a yello sh; brown print.

Example fi The printing paste is prepared witht 7 Parts Potassium saltof 1-aminoanthraquinoneJ-sulfonic ai 1i200% 30 Butyl 'Carbitol- 50 Hotwater, 7 310 Crystalgum 1 :2 w V, 500 Cuprous oxide 111 50 Ammoniumphosphate 3':4= 60 This'paste is printed on a fabric ofpolyacrylonitrile endless filament. The orange-eolored printis finishedas described in the-preceding example. It possesses excellenttastnessproperties.

Example." 7

A printing pasteof:

Parts So m. sal f: 1.4:diaminomthrmuiuone-Z-wlfQniQ acid .15 1:1 mixtureof ethanol and phenol 100 Water 535 Tragacanth 60:1'000 300 Cuprousoxide 1:1 20 Ammonium sulfate 1:2 30

is printed. on slubbing of. polyacrylonitrilestaple. fiber. The'print.is dried;v at; steamed for. 10 minutes at 220? without: pressureand for2.0;minutesat about 265 andiat:1=6-superatmospheriepressure. It; is.then rinsed with. cold, water, soaped at. 1204.40? with. a sulfonatedfatty alcohol, rinsedagain. and: dried. Av violet. print is obtained.which. is fast. to. light, washing and. rubbing. "lihepenetration. ofthe fabric is. very good.

A.padding --liquorof the above compositionis-pad-dyed on a fabr-ic ofpolyacrylonitr-ile endless filamente The pad=dyeing is finished asdescribed in Example 4. his

' blue in' shade aud'is 'fasttollight; washing and-rubbing.

Example 9 A padding liquor containing: Parts Lithium salt of1-amino-4-pheny1aminoanthraquinone-2-su1fonic acid 15 Thiodiethyleneglycol 100 Water 535 Crystal gum 1:2 300 Cuprous oxide 1:1 20 Ammoniumsulfate 1:2 30

is applied upon a fabric of polyacrylonitrile endless filament. Thepadded fabric is dried, steamed for 15 minutes at 260 and about 1.3superatmospheric pressure, then rinsed in cold water and soaped at120-140 with a sulfonated fatty alcohol. After a second rinse anddrying, a blue print is obtained which is fast to light, washing andrubbing.

Example Useful dyestufis for carrying out the process disclosed in theExamples 1 to 9 are also: 7

The copper complex compound of the monoazo dyestuif obtained by couplingdiazotized 1-amino-2-hydroxynaphtha-lene-4-sulfonic acid with1-phenyl-3-methyl-5- pyrazolone (printing and pad-dyeing red shades);

The copper complex compound of the monoazo dyestufi obtained by couplingdiazotized 2-amino-1-hydroxy- 4-chlorobenzene with1-hydroxynaphthalene-4-sulfonic acid (red-violet);

The nickel complex compound of the monoazo dyestuff obtained by couplingdiazotized l-arnino-Z-hydroxynaphthalene-4-sulfonic acid with1-phenyl-3-methyl-5- pyrazolone (ruby).

Having thus disclosed the invention, what is claimed is:

1. A process of printing and pad-dyeing polyacrylonitrile substrateswhich consists essentially of impregnating the polyacrylonitrilesubstrates with aqueous pastes containing a water-soluble organicdyestuff selected from the group consisting of direct dyestufis, aciddyestuffs and metallizable and metallized dyestufis, a water-solubleorganic solvent, a thickener, cuprous oxide and a member selected fromthe group consisting of non-volatile acids and the ammonium saltsthereof, and subsequently drying and steaming the resulting prints andpad-dyeings.

2. A process according to claim 1, wherein the substrate is in fabricform.

3. A process according to claim 1, wherein the substrate is in slubbingform.

4. A process according to claim 1, wherein the metallizable dyestuffscontain lake-forming ortho-hydroxycarboxylic acid groupings.

5. A process according to claim 1, wherein the metallizable dyestuffscontain lake-forming ortho-dihydroxy groupings.

6. A process according to claim 1, wherein the cuprous oxide is appliedin finely dispersed form.

7. A process according to claim 1, wherein the prints and pad-dyeingsare dried at -160 F. and steamed at 220265 F. and at a pH of between 2and 4.

8. A process according to claim 1, wherein the metallizable dyestuifscontain metallizable groupings of the formula wherein x stands for amember selected from the group consisting of a hydroxy, carboxylic acidand amino group.

9. A process according to claim 8, wherein the metallizable dyestuffscontain metallizable groupings of the Formula a as well aslake-forming"ortho-hydroxy-carboxylic acid groupings.

10. An aqueous composition for the printing and paddyeing ofpolyacrylonitrile substrates which consists essentially of awater-soluble organic dyestuff selected from the group consisting ofdirect dyestuifs, acid dyestufis and metallizable and metallizeddyestuffs, a water-soluble organic solvent, a thickener, cuprous oxideand a member selected from the group consisting of non-volatile acidsand the ammonium salts thereof.

11. An aqueous composition according to claim 10, wherein the cuprousoxide is present in finely dispersed form.

References Cited in the file of this patent UNITED STATES PATENTS

1. A PROCESS OF PRINTING AND PAD-DYEING POLYACRYLONITRILE SUBSTANCESWHICH CONSISTS ESSENTIALLY OF IMPREGNATING THE POLYACRYLONITRILESUBSTRATES WITH AQUEOUS PASTES CONTAINING A WATER-SOLUBLE ORGANICDYESTUFF SELECTED FROM THE GROUP CONSISTING OF DIRECT DYESTUFFS, ACIDDYESTUFFS THE METALLIZABLE AND METALLIZED DYESTUFFS, A WATER SOLUBLEORGANIC SOLVENT, A THICKENER, CUPROUS OXIDE AND A MEMBER SELECTED FROMTHE GROUP CONSISTING OF NON-VOLATILE ACIDS AND THE AMMONIUM SALTSTHEREOF, AND SUBSEQUENTLY DRYING THE STEAMING THE RESULTING PRINTS ANDPAD-DYEINGS.